General access to azoles through tailored nitrogen–nitrogen bond construction

Cyclic compounds containing a nitrogen-nitrogen bond are highly significant in chemistry and pharmacology due to their unique structures and versatile chemical properties. The diverse range of available cyclic nitrogen–nitrogen containing compounds offers numerous applications due to their stability, reactivity, and biological activity, making them attractive targets for diverse applications, from materials science to medicinal chemistry. In materials science, their optical and electronic properties make them useful in dyes, pigments, and photoresponsive materials and in medicinal chemistry they provide a foundational scaffold for creating drugs with specific biological functions, particularly in targeting nucleic acids, enzymes, and receptors. However, technologies that enable direct construction of the key nitrogen–nitrogen bond are elusive. Here, this limitation is addressed by disclosing a tailored copper-mediated technology that enables direct nitrogen–nitrogen bond formation from prevalent reagents. The developed process is believed to proceed through a decarboxylative skeletal editing pathway involving both carbon–nitrogen bond cleavage and nitrogen–nitrogen bond construction, offering a modular approach for straightforward access to a wide set of decorated nitrogen-containing heterocyclic scaffolds for widespread adoption.